Method for photoelectrochemical polishing of silicon wafers

ABSTRACT

A method is provided for photochemical polishing of a silicon wafer using electromagnetic waves within the spectrum of 150 to 2000 nanometers wavelength. A photochemical polishing apparatus is also disclosed in which the electromagnetic waves are provided by a waveguide in close proximity to the surface of a silicon wafer electrode.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the polishing of silicon wafers in preparationfor their use in the production of integrated circuit chips.

2. Discussion of Related Art

Silicon wafers for the semiconductor industry must possess a high degreeof surface perfection before they can be useful in the devicefabrication process. These surfaces are universally produced bypolishing the wafer with a polishing slurry. Polishing slurriesgenerally consist of a composition which contains a concentration ofsubmicron particles. The part, or substrate, is bathed or rinsed in theslurry in conjunction with an elastomeric pad which is pressed againstthe substrate and rotated such that the slurry particles are pressedagainst the substrate under load. The lateral motion of the pad causesthe slurry particles to move across the substrate surface, resulting inwear, or volumetric removal of the substrate surface. Ideally, thisprocess results in the selective erosion of projecting surface featuresso that when the process is completed a perfect plane surface isproduced down to the finest level of detail.

The silicon polishing process as practiced in industry consists of twoor more steps. In the first, or coarse polish step, gross defectsremaining from wafer sawing and shaping operations are removed. Thewafer surface appears smooth and specular but still contains numerousminute defects. These defects are removed by subsequent final polishsteps which remove little material from the surface but act to polishaway the surface defects. The present invention relates to thesepolishing processes.

Photoelectrochemical etching of semiconductor materials has beenroutinely carried out to provide holes and trenches in the semiconductormaterial. For example, U.S. Pat. No. 4,482,443, describesphotoelectrochemical etching of N-type silicon using an alcohol basedsolution of hydrofluoric acid as the electrolyte.

It is known that silicon may be removed from the surface of a siliconwafer by photoelectrochemical action. This process has been used formany years to construct holes and trenches on silicon wafers and to makea porous silicon surface structure. If one could use the removal ofsilicon by photochemical action to provide a planarized surface, thiswould allow one to forego a standard polishing process with slurryparticles and polishing pads and, therefore, provide a cleaner surfacefor subsequent processing of the wafer.

SUMMARY OF THE INVENTION

A method for photoelectrochemical polishing of a silicon wafercomprising: placing a silicon wafer in an electrolytic cell as anelectrode and, with an electrolyte comprising a conductive ion as anucleophilic or an electrophilic species, applying a potential to theelectrode while irradiating the surface of the electrode withelectromagnetic waves within the spectrum of 150 to 2000 nanometerswavelength.

Another aspect of this invention is an apparatus for thephotoelectrochemical polishing of a silicon wafer comprising (a) saidsilicon wafer in an electrolytic cell as an electrode, (b) a waveguidewhich provides evanescent radiation of predetermined wavelength(s) inclose proximity to the surface of said silicon wafer electrode, and (c)an electrolyte, in the space between said silicon wafer surface and saidwaveguide, having an absorption coefficient for said predeterminedwavelength(s) such that said evanescent radiation is reduced to at mostabout 10% of its initial intensity over a path length of about 2microns. A further aspect of this invention is a method forphotoelectrochemical polishing of a silicon wafer comprising: placingthe silicon wafer in an electrolytic cell as an electrode, theelectrolytic cell having a waveguide which provides evanescent radiationof predetermined wavelength(s) in close proximity to the surface of thesilicon wafer electrode, the electrolytic cell also having anelectrolyte, in the space between the silicon wafer surface and thewaveguide, having an absorption coefficient for predeterminedwavelength(s) such that evanescent radiation is reduced to at most about10% of its initial intensity over a path length of about 2 microns.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a cross section of an electrolytic cell containing a waveguide.

FIG. 2 shows schematically how light affects the peaks on the surface ofa silicon wafer.

DETAILED DESCRIPTION OF THE INVENTION

A photoelectrochemical cell can be used for the polishing of a siliconwafer in the following way. A doped wafer of silicon of either then-type or the p-type is used as an electrode along with a counterelectrode which might be platinum or any other metal used for thispurpose. The electrode is placed in a container which contains anelectrolyte and electromagnetic radiation in the ultraviolet, visible ornear infra red spectrums is provided to the surface of the electrode.The electrolyte contains a conductive ion as a nucleophilic orelectrophilic species. A potential of a given voltage is applied to theelectrodes while the surface of the silicon electrode is irradiated.

The condition of the surface of the silicon wafer electrode isdetermined by Nomarski microscopy and/or Zygo surface profilometry. TheNomarski pictures show the general condition of the surface includingthe number and size of pits in the surface structure. The Zygoprofilometer can give a quantitative measure of surface roughness as theroot-mean-square of surface variations.

Average removal rate from the surface of the silicon wafer during a testis determined from the weight of the silicon wafer electrode before andafter photoelectrochemical polishing.

EXAMPLES

Stock polished n-type Si was used as an electrode in an electrolyticcell by making ohmic contact with a 2 cm by 2 cm sheet of n-type Si. AnAg/AgCl reference electrode and a Pt mesh counter electrode were used inthe cell. The electrolyte was an aqueous solution of NH₄ F at about 1Molar concentration. Prior to PEC polishing tests the n-type Sielectrodes were cleaned for one minute in a 25% aqueous solution ofhydrogen fluoride. The open circuit dark potential and photopotential ofthe n-type Si electrode in the solution are φ_(d) =-0.635 V andφ_(photo) =-0.590 V, respectively. The light source used was a 250 Whalogen lamp situated at various distances from the electrolytic cell.The silicon removal rate from the surface of the n-type Si electrode wasdetermined from the weight of the electrode before and after exposure toPEC polishing. The n-type Si electrode surface was examined by bothNomarski microscope and Zygo before and after exposure to givenphotoelectrochemical conditions to compare surface roughness. There isan improvement in surface roughness under conditions which give areasonable removal rate of about 0.1 to about 0.3 μm/min.

For example, the following removal rates and RMS surface roughnessmeasurements were obtained on silicon wafer electrodes which prior toPEC polishing were cleaned by using a standard cleaning solution, SC1,for 2 minutes.

                  TABLE 1                                                         ______________________________________                                                Applied Potential                                                                          Removal rate                                                                             TMS                                           Electrode                                                                             (Volts)      (μm/min)                                                                              (A)(80 μm filter)                          ______________________________________                                        before  N/A          N/A        8.21                                          #1      0.90         0.063      8.13                                          #2      1.50         0.085      7.35                                          #3      2.50         0.12       6.90                                          ______________________________________                                    

It is obvious that a smoother surface can be obtained by means ofphotoelectropolishing. This was also shown at higher removal rates byexamining the surface before and after photoelectropolishing by takingphotographs of the electrode surface using a Nomarski microscope.Conditions for these experiments and the results are given in Table 2.

                  TABLE 2                                                         ______________________________________                                               NH.sub.4 F                                                                            Applied                                                               Conc.   Potential                                                                              Time Overall Removal                                  Electrode                                                                            Molar   Volts    min. Rate μm/min                                                                          Surface                                ______________________________________                                        #25    8       0.5      10   0.28      Unimproved                             #27    8       0.5      5                                                            1       0.2      5    0.24      Improved                               #30     4*     0.8      10   0.27      Improved                               ______________________________________                                         *Electrolyte also contained 0.1% piperonal.                              

These results show that the concentration of NH₄ F in the electrolyte ispreferably from about 0.5M (molar) to about 8M. At 8M all samples showedpitting on the surface of the silicon wafer. More preferably theelectrolyte concentration is about 1M to about 5M. And most preferablyit is about 4M.

The results also show that one can also obtain an improved surface when,for example, the silicon wafer electrode is exposed to 8M electrolytefor a time period and then is exposed to 1M electrolyte for anadditional time period. For example, when a wafer was exposed to 8Melectrolyte at a potential of 0.5 volts for 5 minutes and then exposedto IM electrolyte at a potential of 0.2 volts for 5 minutes, the overallremoval rate was 0.24 microns/minute and the electrode surface was lessrough as shown by Nomarski microscope photographs.

Another way to obtain an improved surface is to add a small amount ofsurfactant to the electrolyte. For example, when 0.1% piperonal wasadded to a 4M electrolyte, the resulting surface was much improved asshown by Nomarski microscope photographs. At a potential of 0.8 voltsfor a ten minute exposure the removal rate was 0.27 microns/minute. Itis felt that surfactant of any kind (anionic, ionic, and non-ionic)might be used effectively at concentrations from about 0.1% to about 5%by weight.

In order to be particularly effective in smoothing the surface of thesilicon wafer electrode surface, the illumination radiation may betransmitted in close proximity to the surface of the silicon waferelectrode. This can be provided by using a waveguide for the incominglight which is transparent to the wavelength(s) of interest and whichhas a refractive index greater than that of the electrolyte surroundingit. Simple illumination of light in an ordinary photoelectrochemicalprocess does not yield spatial selectivity because the surfaces of peaksand valleys on the wafer surface will dissolve at the same rate sincereactant concentrations and light intensity are essentially constant atall points. In order to efficiently smooth the surface, improvements tothe basic techniques of photoelectrochemical processing have beendiscovered.

If the illumination is provided by passing the light source through awaveguide structure, some of the light leaks out of the waveguide intothe proximate vicinity of the surface. These are evanescent waves. Theyare significantly increased when the waveguide actually contacts thesurface of the silicon wafer. Thus the peaks which contact the waveguidewill receive more radiation than the noncontacted portions of the wafer.If a particular wavelength of radiation is used, the spatial selectivityof the evanescent waves are increased if the electrolyte absorbsradiation at that wavelength. The percent of radiation transmitted canbe determined by Equation 1.

    % radiation transmitted ν=e.sup.-αCL

where α is the absorption coefficient, C is the molar concentration ofabsorbent in the electrolyte, and L is the path length.

If the electrolyte is highly absorptive, the evanescent radiation canonly react with substrate asperities where L is low and cannot reachrecesses where L is high. By judicious choice of absorption coefficientat a given wavelength and concentration of absorbent, one cansignificantly improve the smoothing effect versus an ordinary PECprocess. One can tailor the absorption of the electrolyte solution bypicking a solvent which highly absorbs a given wavelength of radiationor by the addition of an soluble dye which absorbs a given wavelength ofradiation. A further improvement to this technique will be to vibrate,oscillate or rotate the waveguide in a random fashion to avoid regularpatterns of removal.

Construction of the waveguide can be of any material such as a plasticwhich is used commonly for optical purposes. It is most desirable to usea plastic which is transparent to the wavelength of interest and has arefractive index, n₁, higher than that of the electrolyte, n₂.

A possible configuration for a waveguide and electrolytic cell of thisinvention is shown in FIG. 1. A rotating disc waveguide 1 is shown inclose contact with a silicon wafer 2 which is supported by a carrier 3.These elements of the apparatus are immersed in the electrolyte 4 in acell container 5. A potential is applied between the silicon wafer and acounter electrode 7 in the electrolyte 4. A light source 6 provideslight energy for this photoelectric process.

FIG. 2 shows schematically how the light affects just the peaks on thesurface of the silicon wafer, thereby, smoothing the peaks to provide apolishing action. In this schematic drawing, the waveguide is shown tohave a smooth surface. It would in reality have a roughness probablyabout equal to that on the surface of the silicon wafer. There would,however, be contact of the waveguide 1 and the wafer peaks 9 at manypoints on the surface of the wafer 3 so that evanescent light waves 8would reach the peaks 9 and they would be worn away by thephotoelectrochemical action of the light waves 8 and the electrolyte 4.The reflected light beams 7 within the waveguide provide the evanescentlight waves 8 which exit the waveguide 1 to effect thephotoelectrochemical action.

There are no doubt many other apparatus configurations which might fallwithin the scope of this invention. The invention is only defined by thescope of the claims below:

What is claimed is:
 1. A method for photoelectrochemical polishing of asilicon wafer comprising: placing said silicon wafer in aphotoelectrolytic cell as an electrode and, with an electrolytecomprising a conductive ion as a nucleophilic or an electrophilicspecies, applying a potential to said silicon wafer electrode whileirradiating the surface of said silicon wafer electrode withelectromagnetic waves within the spectrum of 150 to 2000 nanometerswavelength;wherein said photoelectrolytic cell comprises: (a) a waveguide which provides evanescent radiation of predetermined wavelength(s)in close proximity to the surface of said silicon wafer electrode and(b) an electrolyte, in the space between said silicon wafer surface andsaid wave guide, having an absorption coefficient for said predeterminedwavelength(s) such that said evanescent radiation is reduced to at most10% of its initial intensity over a path length of 2 microns.
 2. Amethod according to claim 1 wherein said electrolyte comprises ammoniumfluoride at about 0.5 molar to 8 molar concentration in water.
 3. Amethod according to claim 2 wherein said electrolyte further comprises asurfactant at about 0.1% to about 5% by weight.
 4. A method according toclaim 3 wherein said surfactant is piperonal.